Adsorption process



May 19, 1953 c. H. Q.. BERG AnsoRP'rIoN `PROCESS Filed Dec. 13, 1947 1N V EN TOR.

By aga? Patented May 19, 1953 UNITED STATES PATENT OFFICE ADSORPTION PROCESS Clyde H. O. Berg, Long Beach, Calif., assigner to Union Oil Company of California, Los Angeles, Calif., a corporation of California Application December 13, 1947, Serial N o. 791,640

(Cl. 18S- 4.2)

21 Claims.

` The present invention relates to the separation of gaseous mixtures by continuous selective adsorption on solid granular adsorbents and more particularly is concerned with the treatment-of gaseous mixtures to separate the more readily adsorbable constituents from the less readily `adsorbable constituents present. More specifically this invention relates to a method and apparatus for the dehydration of gases or gaseous mixtures such as the dehumidication of air in air conditioning operations by selective adsorption and may be applied to the dehydration of substantially any gaseous mixture. It is to the art of gas dehydration or dehumidication that this invention is particularly directed.

iv Gases containing water vapor are often encountered in industrial operations and in many such operations the presence of the moisture is detrimental or undesirable. The presence of water vapor in natural petroleum gases which are processed under elevated pressures and temperatures often causes the formation of hyyd'rocarbon hydrates which are solids at these which either react with or are corrosive in the presence of water vapor is highly desirable in many industrial operations.

` Of particular importance is the dehydration and dehumidification of air as required in air conditioning operations which may be carried .out in conjunction with industrial processes .wherein certain materials must be handled and treated under controlled humidity conditions. For example, in the preparation of various bers including pulp, news print and other types of paper, synthetic ber including viscose, rayon, nitro-cellulose and cellulose acetate, natural silk, hides such as sheep skin, other materials including confections, tobacco, and preparation of electrical cable, the manufacture of cereals, certain operations involved in packing and printing and in many other industrial operations controlled..l

humidity conditions are required. The dehumidii'ication of air is further of importance in the maintenance of comfortable conditions in public and domestic buildings. There has been established a denite relationship between the air humidity and the air temperature in which individuals feel comfortable. In geographical areas wherein the temperatures and humidities are both high, air conditioning which involves dehumidication is a prime object in the attainment of comfortable air conditions. It is, therefore, primarily to the conditioning of air that the present invention is directed.

One object of the present inventionis to provide a method and apparatus for the separation of gaseous mixtures which contain constituents of varying degrees of adsorbability into substantially pure fractions by selective adsorption.

Another object of this invention is to provide a method for the separation of such more readily adsorbable constituents as water vapor from gaseous mixtures containing water vapor by contacting such gaseous mixtures with a continuously moving bed of solid granular adsorbent.

It is a particular object of this invention to provide an improved method for the dehumidification of air by the continuous selective adsorption process' to forma dehumidified air having 4the desired moisture content for either industrial or domestic use.

It is another object of this invention to provide an improved method for controlling air humidity by employing the principles of selective adsorption in a dehumidication process.

An additional object of this invention is to provide an apparatus adaptable to accomplish-the above-mentioned objects.

Other objects and advantages of this invention will become apparent to those skilled inthe art as the description thereof proceeds.

Briefly, the present invention comprises a process for the separation of gaseous mixtures by continuous selective adsorption on solid granular adsorbents and which is particularly adaptable to the separation of water vapor from moisturecontaining gases. Ihese separations are accomplished by contacting the gaseous mixture to be separated with a continuous moving bed of a solid granular adsorbent wherein the more readily adsorbable constituents of the gaseous mixture, in this case water vapor, are adsorbed leaving the less readily adsorbable constituents of the gaseous mixture as a substantially unad'sorbed gas. The ability of the selective adsorption process to eiect such separations as the 3 separation of water vapor from less readily adsorbable constituents is based upon the fact that lsolid granular adsorbents exhibit a preferential adsorption. Certain gas molecules are adsorbed and held more strongly than otherl gases, the latter may be termed the less readily adsorbable constituents. By a continuous sequence of adsorption and desorption operations which are conducted continuously within a dense phase of solid granular adsorbent as a moving bed, a substantially complete and efcient separation of the gaseous mixture may be effected. In the case of the separation of moisture from humid air, a substantially complete dehydration may vbe effected, if desired, or by properly controlling the operating conditions such as the temperature and pressure and the ratio of adsorbent to feed gas to be dehydrated, a gas may be produced having any moisture concentration between that of the feed gas to be treated and a substantially completely dehydrated gas. A rich adsorbent containing the adsorbed moisture is formed with the dried air. The rich adsorbent is subsequently heated and contacted with a portion of the humid air feed as a stripping gas which desorbs the adsorbed moisture and leaves a lean adsorbent ready for reuse.

Dehumidified gases may be produced having dew points as low as about 100 F. or lower. When it is desirable to substantially completely dehydrate a given gaseous mixture such as air, natural gas or other moisture-containing gas, the ratio of pounds of adsorbent per MSCF (1 MSCF is equal to 1,000 standard cubic feet) vof anhydrous gas is increased to a value higher lthan that required when a gas having a certain dew point or certain 'humidity is desirable. The continuous selective adsorption process as hereinafter more fully described offers a simple, efficient, and easily controlled method for regulating the moisture content of substantially any gas-ecus mixture and lends itself extremely well to dehumidiica- 'tion loperations involved in air conditioning of domestic, public, and industrial buildings.

The process and apparatus of this invention may perhaps be more clearly understood by reference to the accompanying `drawings 'in which:

Figure 1 represents a vertical cross'section of a selective adsorption apparatus which Yis adapted to the dehumidification of large quantities vof hydrous gases, and

Figure 2 which shows a vertical 'cross section of a relatively small scale apparatus suitable, for example, to the Idelfiurnidiioation of air for domestic purposes.

Referring now more particularly to Figure 1, selective adsorption column 'lb is provided with hopper H, cooling zone I2, lean or Adry gas disengaging zone lseparation or adsorption zone I4, feed gas engaging zone i5, desorption zone 15, adsorbent now control zone il, vand bottom kzone Hl. A continuous flow of a solid granular adsorbent is maintained from hopper Ii dow-nwardly through `the aforementioned zones which collects in bottom zone i8. The solid Vgranular adsorbent collect-ing therein is removed by means of lline 19 to flow through adsorbent flow control valve 2l! which in turn is actuated by level control 2l. A level control mechanism which is suitable for application is more `completely disclosed, illustrated vand claimed 4in cao-pending kapplication, Serial No. 775,554., .filed `September 22, 19.47, vnow U.. S. Patent No. 2,590,148. The level control mechanism 2l operating in conjunction with .adsorbent flow controller I7 yeffects an yaccurate volumetric control over the flow rate of the adsorbent passing downwardly through selective adsorption column Ill. The adsorbent passing through valve 2S is conveyed by means of transfer line 22 and is introduced into lift line Z3 wherein a suspension of solid granular adsorbent is formed with a lift gas which may comprise a portion of the gaseous mixture to be separated or dehydrated. This lift gas-adsorbent suspension is conveyed under pressure exerted by blower 24 controlled by valve 25 upwardly through lift yline y23 and is introduced into impactless separator 26. Herein the suspended adsorbent is separated from the lift gas and subsequently flows substantially independently of the lift gas downwardly through transfer line 2 to be introduced into the upper portion of selective adsorption column Hl. The separated adsorbent settles as indicated in hopper Il to subsequently low downwardly through selective adsorption column l0 as described.

The .impactless separator 25 is more clearly de. scribed, illustrated and claimed in oo-pending application, Serial No. 618,345, iled September 24, 1945,.,now abandoned. The solids feeder present in solids feeder zone Il is more clearly described, illustrated and claimed in co-pending application, Serial No. 618,347, also filed Septomber 24., 1945, now U. S. Patent No. 2,544,214.

In order to facilitate a clear description of the apparatus illustrated inFigure l, the gaseous mixture to be dehydrated will be assumed to be humid air and the solid granular adsorbent em- -ployed to effect the dehydration will be assumed to be activated charcoal.

Returning now to Figure 1, the humid air is introduced by means of line 28 into blower 24 and is passed at somewhat increased pressure into manifold 2S. A portion of this air may be passed as previously described through line 3D controlled by valve 25 and employed as the lift gas to convey activated charcoal from the bottorn to the top of the selective adsorption column. The remaining portion of the air is passed by means of vline 3l controlled by valve 32 through line 33 `into blower 34. Herein the pressure of the air is increased and the compressed air is passed by means of line 35 controlled by valve 36 in-to feed rgas engaging zone l5. 'I'he major portion of the feed gas `thus introduced into feed gas engaging zone l5, passes upwardly through adsorption zone |14 countercurrently to a downwardly moving bed of activated charcoal. Sepa.. ration zone M may be advantageously provided `with :a plurality of adsorption zones when substantially complete gas dehydration is desired. -Snoh a separation Zone is `more clearly described, illustrated, and claimed in co-pending application, Serial No. 730,166, filed .February 21, 1947, now U. S. Patent No. 2,550,955. An intimate Contact of the humid nir to be dehydrated is thus obtained and the water vapor present vis substantially completely .adsorbed to form a rich Acharcoal leaving 4lair substantially unadsorbed and dehumidied. The dehumidified air passes upwardly to disengaging zone I3 and a portion is removed therefrom by means .of line 3l .controlled by `valve 38. 'The dehnmidied air thus removed is passed by 'means of .line 38 into separator 4U wherein .traces of suspended charcoal vare removed. The charcoal fines thus lseparated are removed from :separator M3 :by means yof line 4| controlled by valve 42. The dehumidied air, substantially free `of suspended vcharcoal lis removedf-rom :separator il by means Vof line yt3 and .introduced into feed gas engaging Zone I5.

'is' sent to fulfill requirements for which it was prepared.

f The rich charcoal containing adsorbed water vapor and heated slightly due to the heat of adsorption liberated passes downwardly through adsorption zone I4 over finned-tube coils I4a through which a cooling medium may be circu- -lated'if desired. The heat of adsorption may thus be dissipated, lowering the rich charcoal temperature, and increasing its adsorption capacity. The cooled rich charcoal passes through feed gas engaging zone I5 into desorption zone -I6 wherein the rich charcoal is subjected to in- -direct heating which increases the partial pressure in equilibrium with the rich charcoal. Operation of the selective adsorption apparatus is such that the remaining portion of feed gas introduced into feed gas engaging zone I5, which portion does not pass upwardly through radsorption zone I4, passes downwardly through desorption zone I6 so as to continuously remove water vapor desorbed from .the rich charcoal.

Such a downward iiow of air is effected by maintaining a pressure in bottom zone I8 which is slightly less than the pressure of the feed gas BY controlling valve 38 the pressure of the gas pres- -ent at lean gas disengaging zone I3 may be made 'sufficient to cause the major proportion of the feed `gas introduced to oW upwardly through adsorption zone I4 while allowing a minor portion, which is sucient to effect water vapor desorption, to owdownwardly through desorption 'zone I 6.

The water vapor desorbed from the rich charcoal in desorption zone I6 passes downwardly -into adsorbent feeder zone I1 vas a rich or wet gas. If desirable, this Wet gas may be removed by means of line 44 controlled by valve 45 and may be introduced into manifold 46. Removal of vthe rich gas through line 44 has the advantage that it prevents a downward flow of gas through adsorbent feeder zone I1 which may in extreme -cases alter the ow characteristics of granular solids through the tubes. Ordinarily this effect vunder these conditions is not pronounced and the :rich gas may also be removed from bottom zone I8 by means of line 41 controlled by valve 48.

:In any event, the rich gas thus produced is introduced by means of line 49 into separator 50 wherein suspended fine particles of charcoal are separated. These particles are subsequently removed from separator 50 by means of line 5I `vcontrolled by valve 52. substantially free of suspended charcoal fines, vis removed from separator 53 through line 53 and is sent to storage or further processed or vented to the atmosphere by means not shown.

The rich gas or wet gas,

The charcoal collecting in bottom zone I8 contains small quantities vof adsorbed moisture and may be termed a partially stripped charcoal. By

4the means previously described, this charcoal is vremoved from bottom zone I8 and is introduced into the upper portion of selective adsorption column I3 to flow downwardly through cooling lective adsorption column Iii. With air and water vmeans of line 56 into separator 57.

6 water or other cooling medium on the outside of the tubes. The cooled lean charcoal subsequently passes into adsorption zone I4 to contact and dehumidify further quantities of humid air.

The moisture desorbed from the partially stripped charcoal passing through cooling zone I2 passes as a vapor into the upper portion of selective adsorption column III wherefrom it may be removed together with the lift gas by means of line 54 controlled by valve 55 and passed by Separator 5l effects the removal of suspended particles of charcoal from the gas stream, which particles are removed from separator 5T by means of line 5B controlled by valve 59. The Wet gas is removed from separator 5l substantially free of suspended charcoal by means of line 60.

This gas comprises a wet gas or humid air but which contains considerably less moisture than the Wet gas removed from separator 5Fl. If desired, these two wet gas streams may be combined and vented to the atmosphere or sent to further processing or storage, not shown.

In large installations it is nearly always desirable to reprocess the wet gas above described as being removed by means of line 60 vin which case Valve 55 is at least partially closed and the stripped gas together with the lift gas is removed from the upper portion of selective adsorption column I0 by means of line 5I controlled by valve 52 and is conveyed by means of line S3 back to blower 24 wherein it is combinedwith the humid air or other gaseous mixture to be dehydrated.

In some instances, not always connected with the dehumidiiication of air, it is desirable to maintain the lift gas circulating v"in a manner which is substantially completely independent of the feed gas to be dehumidied. In such a case valve 32 is 4closed and the feed gas to be dehumidiiied is introduced by means of line 54 controlled by valve directly in to manifold 33 and the air is blown by means of blower 34 through line 35 for introduction into feed gas engaging zone I5. In this manner the recirculation of a lift gas to maintain the charcoal circulation is employed which is substantially independent of the other gas streams involved in the process. However, a small amount of lift gas passes upwardly through transfer line 22 countercurrent to the downwardly flowing charcoal and a small amount of wet gas passes downwardly from bottom zone I8 through sealing leg I5 concurrently with the downwardly owing charcoal. In order to prevent contamination of the lift gas or of the wet gas, bleed line 55 controlled by valve 61 is employed to remove a seal gas from charcoal flow control valve 2U thus effectively sealing the bottom portion of the selective adsorption column against contamination and against loss of wet gas. y

The control of the process may be effected by employing temperature recorder controller 68 which serves to actua-te control valve 36 to vary the quantity of' feed gas introduced into a sevapor mixtures, the water vapor is the more readily adsorbable constituent and is adsorbed in adsorption Zone I 4 with the liberation of heat. The heat of adsorption causes the temperature of the adsorbent to rise and leads to the formation of a temperature break or a sharp temperature gradient within the adsorbent in that zone. The positioning of thermocouple point 59 or other suitable temperature sensitive means in contact Ygaging zone l5.

with the vcharcoal in vadsorption zone -I4 Jpermits temperature recorder controller 53 to be used to factuate `control valve 36 in accordance with the position of the temperature .breakin the 1adsorp- .in a substantially anhydrous conditioner in .a

condition of any desired humidity.

Referring now more particularly to Figure .2,

4a vertical cross section of a Vmodiiieol selective .adsorption ,apparatus is shown which vis, adapted to a small scale dehydration of gases Aand which will accomplish the sameseparations as .the apparatus described andillustrated Figure 1. An apparatus such as that shown in Figure 2 is more readily adaptable to domestic dehumidiiication operations and to the vair conditioning of small buildings. `Such an apparatus is further suitabie for the dehydration of other ygases in small quanu -tities The characteristic feature .of this appa ratus which dierentiates it from the apparatus of Figure l is the fact that .an external .lift line vis not employed and that the charcoal or other adsorbent is conveyed `from the bottom .of the vessel to the top of the vessel by means of a conduit positioned within the vessel itself. Such a design readily lends itself to the simpliiied .coni;

struction desirable in 'small installations.

Selective adsorption column 'ill is provided with hopper 1l, cooling zone T2 and a separation cone which employs a modication somewhat different from thatshown in Figure 1.

adsorption zones present in the separation zone. As shown yin Figure .2 these two adsorption zones function as `one separation zone and are in effect connected in parallel so that each handles about one-half of the quantity of feed gas to be separated. Multiple adsorption zones may be lein- `ployed wherein the rich charcoal formed in vone is conveyed independently of the other to the vdesorption zone.

`1947, now U. S. Patent No. 2,559,955. The primary adsorption zone 13 is .provided with primary lean gas disengaging zone M and primary `en- .Secondary adsorption zone l is provided with secondary lean gas disengaging zone l? yand vsecondary feed gas engaging zone .18. The Yadsorption Ione may also be provided 'with'means lfor cooling the charcoal in situ to dissipate the heat of adsorption. Such means in the form of :coiled nned tubes are Vshown in the iadsorptionzone of Figure -l. Selective adsorption `column lll vis further provided with desorption zone 'i8 and bottom zone 3@ which latter zone containsa modified charcoal control valve adapt- Dual `inlets land `outlets are shown so `that in eiect there are two Such modifications are described, illustrated and claimed in copending application, Serial No. 730,166, led February 21,

valve 81 wherein it is vengaged with .the lift .gas and raised through lift line 82 to impactlessseparator '83* Herein the suspension is broken and the separatedcharccal settles into hopper l l.

Thelfee'd gas may in one modification 4be introduced bymeans -oi line 84 and passed through blower 85. The compressed air then .may .be divided into two streams, the first of which passes by means of Aline 86 controlled lby valve B7 .and-is introduced by means of line B8 upwardly through bottom zone 30 .into charcoal flow control valve 8|. This 'valve may consist .of a movable member 89 adapted tobe raised and lowered by .motive means' 'so that theliit gas introduced by means of .line ,B8 .may pass upwardly therethrough and so thatxa'varying quantityof charcoal may be suspended depending on the position of movable means :89. lThe remaining quantity of compressed .air is .passed by `means 4or line 9i controlled'by valve 92 into manifold 93. Here again `the gas may be divided linto two streams, the

.nrst of which is introduced by means of line :94 controlled .by `valve 95 into primary feed gas en gagging zone l5, and the secondis passed'by means of line 96 `controlled by 4valve l91 'into secondary reed gas engaging '.zone la. Each fraction 'of feed gas thus introduced passes upwardly through the respective vadsorption zone in direct countercurrent contact Ywith .the downwardly flowing `charcoal. The humidity of the vlean gas 4disengagedirom the charcoal in primary lean gas rdis engaging zone it and :secondary lean :gas vdisengaging zone ii depends lupon the temperature of the charcoal and the ratio of the ows of charcoal yand feed gas. 'Theseilean gases are removed Vby means of linesailaand .99 controlled respectively by valves lli and l0! and are combined in manifold H32. The lean dry gas is introduced by `means of' line lila 4into separator wat wherein suspended .charcoal particles are separated. The charcoal particles are Vremoved therefrom by means of vline its controlled by valve IBS and .the lean dry gas or dehumidiiied air is removed by means of line lill and vsent to `the use for which itzis intended, not'shown.

Since the charcoal which has adsorbed 'moisture in primary adsorption zone i3 ultimately hows downwardly lthrough secondary adsorption zone 12 in .themodication zone in Figure 2, the ,quantity vvof moisture `adsorbed in the latter aclsorption Vzone will be less than the l:former for vequal quantities of gas :passed .through each'adsorption zone. Consequently, the humidity of the lean gas .removed from secondary disengag'ing .zone 'il may 'he somewhat vhigher than that re- `dry gas produced will result in-a product having the desired composition.

The rich or wet charcoal form-ed in the separation icone as above described passes downwardly into desorption zone 19 which is provided with means 'for heating the charcoal and which in small selective adsorption columns .may be best provided by :means oi a coiled 'nned tube The used of finned tubes is desirable since an `e'iiicient heat transfer `between the heat transfer medium and the rich wet charcoal 'is thereby effected. Particularly is this true when the fins are formed 'on the tube as a spiral or as a series oi ydiscs quite closely 'spacedalongthe length of the tube so that the rich charcoal flows downwardly around the tubes and between the uns. The heatingmedium may comprise steam or hot water passed through the tubes or diluted flue gases may be employed. It is also possible to extend resistance coils through theA tubes so that the heat may be producedelectrically within desorption zone l; By any of these aforementioned means Athe temperature of the rich or wet charcoal isy increased to a temperature of between about 200 F. and about 500. F. or higher and a continuousl downward flow of a portion of feed gas introduced into secondary engaging zone 'I8 is maintained through desorption zone 19 concurrently with the downwardly flowing charcoal. By this means a portion of the adsorbed. moisture is desorbed and swept out of the desorption zone to be combined with the lift gas and raised to the upper portion of selective adsorption zone 10. The partially stripped charcoal settles into hopper 'Il while thelcombined stripped gas and lift gas is removed from Vthe upper portion of selective adsorptio column l0 by means ofline |08. l

.The partially stripped charcoal passes downwardly from hopper 'il through cooling zone 12 which may be adapted with finned tube coils similar to those employed in the adsorption zone previously described. The charcoal passes downwardly around the tubes and between the ns and is cooled by indirect heat exchange with a cooling medium such as cold water circulated through the tubes. A portion of the lean gas product normally removed from lean gas disengaging zone 'I4 is allowed to pass upwardly in direct `contact'vvith charcoal flowing downwardly through cooling Zone 12 in order to strip remaining quantities-fof. adsorbed moisture from the charcoal to form a cooled lean charcoal.` The water lvapor thus desorbed together with a small portion of lean gasis combined with the lift gas and stripped gas previously described in the upper portion of selective adsorption column and the combined streams are removed by means of line 108 controlled by valve |09 and introduced into manifold H0. Proper adjustment of valves |00 and 09 permit the upward ow of a sufficient amount of lean gasthrough'cooling zone 12 to effect desorption'of the remaining quantities of adsorbed water vapor. These conditions are similar to those employedfin regard to valves 81 and 97 and the bottom portion of selective adsorption column 10 for the control of a small amount -of stripped gas passing downwardly through desorption Zone 10. Similarly controlled conditions were described above in connection with Figure l. k v

The combined gas stream yintroduced into manifold H0 may be removed by means of line l l l controlled 'by valve- I I2 and-passed into separator lf3 for the separation of suspended charcoal particles. These particles may be removed fromV separator H3 by means of line 4H4 controlled by valve H5. The combined gas, thus freed of suspended solids may be removed as a wet gas by means of line H5v and sent to storage or further processing, not shown, or vented to the atmosphere. In some cases it may be desirable to reprocess a portion of this gas in which case valve H2 is at least partially closed and valve Il] is at least partially'opened so thata portion of the combined gas may be returned by means of line H8 and combined with the gas flowing thro-ugh line 34, the inlet line of blower 05. `1t may also be desirable as previously described in connection with Figure l that the lift gascycle and the feed gas streams be maintained substantially independent. In this case valve 92 is at least partially closed and-the feed gas is introduced by means of line H9 -controlled by valve |20 and passed by means of blower 12| into manifold 93 for introduction into the separation zone. Y

The apparatus just described in connection with Figure 2 is actually a modification of the apparatus shown in Figure 1 but which is particularly adapted to smallscale sizes and constructions. Both described apparatuses have been found capable of effecting` ecient separations of gaseous mixtures and in particular have been found to be well adapted to the separation of water vapor from various gases such as, for example, air. The conditions necessary for the dehumidiiication of air, for example, by the method and apparatus of this invention will be" more clearly defined in connection Withthe following examples: 1`

Efcample I To illustrate the application of the process and apparatus of the present invention, conditions are herein described for the dehumidication of 300,000'cubic feet of air per hour, or 5,000 cubicv feet per minute. The incoming airis at a tem-'-A perature o'f 85 F. and awet bulb temperature'of 77 F.- and a relative humidity of about 70%. The humid air thus contains slightly more than 2.8% moisture, by volume. It is desired to substantially completely dehumidify air at this rate and an apparatus s'irnilar'to that shown in Figure 1 of the accompanying drawings is employed with the exception that a plurality of independent adsorption zones are used. `This is done in order to decrease the diameter required for the'selective adsorptionY column in dehumidifying this' o luantity-ofr air. For' example, if only one'ad-l sorption zone were'employed a selective adsorpe tion column having va diameter of about 12.5 feet is required in order that the 'gas velocity existing within the adsorption zone is not unduly high. By employing three adsorption zones each provided with va gas inlet and outlet and a charcoal inlet and outlet 300,000 cubic feet per hour of air may be dehumidied in a selective'adsorption column vhaving a diameter of 7 feet 3 inches. The

, total height of such'a column is between about 95 lfeet'and 100"feet. The activatedcharcoal circulation 'of about 1200 pounds per'hour is 'employed for a charcoal-gas ratio of 40 pounds of charcoal per MSCF of air (l MSCF 'is equal vto 1,000 standard cubic feet), a lean gas or'dry gas comprising'dehumidied air is removed at a rate of 280,000 cubic feet per hour andy has a dew point of '-80" F. The combined wet gas'streams containv about H1/2%' water vapor and 'are removed at a rate of about 20,000 cubic feet per hour; The charcoal is heated to a' temperature 'of 800 F. in the desorption zone in order to effect a substantially complete desorption of adsorbed water vapor.

The air having a dew point of F. is substantially completely dry. By decreasing the charcoal-air ratio from 40 pounds per MSCF to lower values such as between about10a'nd'20 pounds'per MSCF Vdry air having humidities between 5% and 25% may be directly produced from the apparatus. If it is desirable that air streams having various moisture contents be produced, a large quantity of air may be substantially completely dehumidied, passed through line 43a and subsequently blended with a portion of the wet gas owing throughnline 53a or `with further quantities of atmospheric air flowing through line a to form air having the required relative humidity as indicated in Figure 1. One of the greatest advantages of producing de humidified air directly from the selective adsorption column is that odors, suspended solids, gascous irritants, etc., which are undesirable in air employed. in air conditioning of buildings are completelyk removed forming a pure, clean and healthful atmosphere,

Example II TheA processv and apparatus of this invention may further be applied: to the treatment of natural gas containing moisture to eifectively eliminate the possibility of solid hydrocarbon-hydrate formation which has a detrimental effect on valves, pumps and piping employed in natural gas transportation. For the dehydration of natural gas charcoal-gas ratios of about lpounds per MSCE or less may be employed depending almost entirely upon the quantity of water vapor present in the gasand` the pressure at which dehydration is to be effected. Increases in dehydration pressure markedly decrease the car bon-gas ratio. required to effect dehydration but also simultaneously increase the temperature-re quired tov effect a desorption of adsorbed water vapor. For'example, dehumidiiication of natural gas containing about 2% by volume of water vapor may be eiected if desired lat atmospheric pressure and employ a charcoal-gasratio of about 45 poundsper MSCF. Stripping temperature lof. about 300 F. is'adcriuateV to desorb moisture from the carbon.. By increasing the pressure of operationto about 100` pounds per square inch gauge, a charcoal-gas. ratio of about 30 pounds per MSCF is adequate to substantially completely dehydrate; the gas and a stripping temperature of about 400 F. isI required to regenerate the caiV bon. Such an increase in pressure decreases the required cross sectional area of the selective adsorption column to about 20% of the area required for` dehydration operations at atmospheric. pressures. This obviously is a pronounced advantage of operation under pressure.

In the dehydration of natural gas an effect not noted inv air dehydration is found in that in the adsorption zone or zones both water vapor and heavier hydrocarbon constituents suchas butanes aresimultaneously adsorbed to form a. rich charcoal.

Inv the dehydration of 250,000v cubic feet of humid natural gasper hour a charcoal rate of 30 pounds per MSCF is employed involving a charcoal circulation rate of '7500- pounds per hour. A selective adsorption column similar to that emplayed: in the apparatus of Example I in that it has three adsorption zones may be employed in the dehydration of natural gas. Such a column for the present example will have: a diameter of about 3 feet 2 inches and, willv stand about '75 feet in height. The dew point of the natural gas product maybe of the orde-1l of 120 F.

Marked reduction in the cross sectional area of the selective adsorption columnr employed in dehydration of such gases with an increase in operating pressure is readily observable by comparison. of Examples I and II. Since air required for air conditioning purposes is not available generally at an elevated pressure Example I has been included as illustrative of atmospheric pressure operations and since natural gas containing water vapor is nearly always available in reineries at elevated pressures or must be compressed to ele vated pressures for transmission, Example II has been includedv as illustrative ofthe more elevated pressures of operation. It is to be under--` stood, however, that pressures considerably higher than those of Example II may be employed to some advantage` as the present invention is notte be limited to the pressures shown in the twov examples described.

Although the present invention has been described particularly in the separation of water vapo-r from air, the method and apparatus are obviously applicable also to the separation of Water vapor from a wide variety of other gases without undue modification. Since water vapor in general is more readily adsorbable than other normally gaseous constituents, the process andapparatus of this inventionl are also applicable to the separation of gaseous mixtures which do not contain Water vapor but which do contain a smallI proportion such as less than about 10% to 201% by volume of more readily adsorbable constituents. Such gaseous mixtures are exemplied by methane containing small quantitiesv of propane, small quantities of methane in hydrogen, small quantities of nitrogen in helium and a number of otherv such gaseous mixtures.

This invention has been described' as employing charcoal as the adsorbenty which is` used: to eiect the separation. Activated charcoal preterably granulai` of about l0 to 20 mesh in size and preferably prepared from coconut hulls or fruit pits comprises the preferred adsorbent. The term charcoaly used in this description is.. however, usedbroadly iny that. any animal, vegetable or mineral carbon. having adsorbent properties may be employed. Furthermore, granules as'large as about 4 mesh or as small as about 100 mesh or smaller may be employed if desired in specic instances. Granular adsorbentsk other than char coal.: may be employed in the method and apparatus of this invention, such adsorbents including activated aluminum oxide, silica gel, activated bauxite', or other adsorbents prepared from metal oxides or metal: hydroxides'.

A modification in the apparatus of this invention and particularly with the modication described in connection with Figure l is possible in the replacements of the lift line shown with a systemA involving. bucket elevators. Bucket ele vators are very suitable in this service at low operation pressures, but lare considerably more noisy and difficult to maintain at higher operation pressures andthe gas lift line shown and described is preferable.

The method and apparatus of this invention is adapted to eiIec-t separations of gaseous mixtures of pressures of from atmospheric or somen what below to as high as 1,000 pounds per square inch or higher. Operations for eiIecting the dehumidication of air are very eiectively accomplished at between atmospheric or about pounds per square inch. The dehydration of natural gas, for example, may conveniently be carried out at pressures. of 50 and 250 pounds per square inch or even as low as atmospheric pressures.

Having described and illustrated my invention and realizing that many modifications may be made by those skilled in the art without depart ing from the spirit andv scope of the following claims, I claim:

la A method for the separation of a gaseous mixturel which comprises passing a solid granular adsorbent downwardly successively through an adsorption zone and a desorption zone as a mov- -13 i-ng'b'ed, introducing said gaseous mixture into contact with said adsorbent whereby a rst portion passes countercurrently through said adsorption zone wherein the more readily adsorbable constituents are adsorbed to form a rich adsorbent and leaving less readily adsorbable constituents as a substantially unadsorbed lean gas and a second portion passes concurrently With said rich adsorbent through said desorption zone, subjecting said rich Kadsorbent therein to indirect heating while directly contacting the thus heated rich adsorbent concurrently with said second portion of said gaseous mixture Vin the absence of other stripping gases thereby desorbing more readily adsorbable constituents to form a rich gas and a partially stripped adsorbent, subsequently indirectly cooling said partially stripped adsorbent in a cooling zone while contacting it with a portion of said lean gas to form a lean adsorbent, and returning said lean adsorbentto said adsorption zone.

2. A method according to claim l wherein said more readily adsorbable constituent in said gaseous mixture comprises water 'vapor'.

3. A method according to claim l wherein said gaseous mixture comprises natural petroleum gas containing water vapor. I

4. A method according to claim 1 wherein said gaseous mixture comprises air containing water vapor.

5. A method according to claim 1 wherein said solid granular adsorbent comprises activated charcoal.

6. A method for the dehumidication of air to eiect conditioning thereof which comprises passing a moving bed of activated charcoal downwardly through an adsorption zone and a desorption zone, introducing said air into contact with said bed of charcoal whereby a portion of said air passes upwardly through said adsorption zone and the remaining portion passes concurrently with the charcoal downwardly through said desorption zone, removing a portion of dehumidified air from said adsorption zone, controlling the rate of ilow of air into said adsorption' zone in accordance with the temperature of said adsorbent therein to maintain a predetermined humidity of said dehumidied air, heating said adsorbent in said desorption zone indirectly while stripping the heated adsorbent therein with said remaining portion of air to desorb adsorbed water vapor leaving a hot charcoal, removing the thus desorbed water vapor from said desorption zone, indirectly cooling said hot charcoal in a cooling zone while countercurrently contacting it with the remaining portion of `said. vdehumidied air forming a cool charcoal and returning said cool charcoal for repassage through said -adsorption and desorption zones.

v'7. A method for the dehumidiiication of humid air which comprises introducing said humid? air into contact with a moving bed of activated charcoal whereby a first portion of said air passes countercurrently through an adsorption zone thereby adsorbing at least a portion of the water vapor contained therein leaving dehumidied air substantially unadsorbed and forming a rich charcoal warmed by the liberated heat of adsorption and a second portion passes concurrently with said rich charcoal through a desorption zone, cooling the thus warmed charcoal in said adsorption zone, removing a portion of said dehumidiiiedv air from said adsorption zone, passing said rich charcoal to said desorption Zone,

heating said rich charcoal by indirect heat ex- 14 change in said desorption zone while concurrently stripping the thus heated charcoal throughout said desorption zone with said second portion ofsaid humid air as the stripping agent to desorb the adsorbed water vapor as a rich gas and leaving a hot partially stripped charcoal, passing said partially stripped charcoal suspended in a lift gas from-said desorption rzone to a cooling zone, cooling said partially stripped charcoal by indirect heat exchange while coun-A tercurrently contacting said partially stripped charcoal as a compact moving bed with the remaining portion of said dehumidiiied air to form a cool lean charcoal and returning said lean charcoal to said adsorption zone.

8. A method according to claim 7 wherein a pressure of between less than about atmospheric pressure and as high as about 1000 pounds per square inch is maintained in said adsorption zone. I I

9. A process for the separation of a gaseous mixture which comprises establishing a cooling zone, an adsorption zone and a desorption zone, passing a moving bed of compact solid granular adsorbentl downwardly successively through said zones, recirculating adsorbent removed from said desorption zone to said cooling zone by suspension in a recirculating gas stream, passing a gaseous mixture to be separated into contact with said adsorbent whereby a iirst portion of said gaseous mixture flows countercurrently to said adsorbent in said adsorption Zone forming a rich adsorbent containing the more readily adsorbable constituents leaving a substantially unadsorbed lean gas and a second portion of said gaseous mixture passes concurrently with said rich adsorbent through said desorption zone, controlling the rate of flow of said gaseous mixture introduced into said adsorption zone in accordance with the temperature-of the adsorbent therein to maintain a predetermined concentration of more vreadily adsorbable constituents in said lean gas, removing said lean gas from said adsorption zone, indirectly heating said rich adsorbent in said desorption Zone while stripping the heated adsorbent therein with said second portion of said gaseous mixture to desorb a rich gas product containing said more readily adsorbable constituents leaving a hot partially stripped adsorbent,

subsequently stripping said partially stripped ad-Y sorbent in said cooling zone with a portion of said lean gas to de'sorb residual quantities of said more readily adsorbable constituents from said adsorbent While indirectly cooling said adsorbent forming a cool lean adsorbent and passing said cool lean adsorbent into said adsorption zone to contact further quantities of said gaseous mixture,

10. A process according to claim 9 wherein the concentration of more readily adsorbable constituents in a gas product containing said uri-.- adsorbed lean gas is maintained at a predetermined value by controlling the ratio of the low of said adsorbent to the ow of said gaseous mixture through said adsorption zone so as to adsorb a desired amount of said more readily adsorbable constituents from said gaseous mixture.

l1. A process according to claim 9 wherein said adsorption zone comprises a plurality lof adsorption zones together with the steps of passing said adsorbent successively through said adsorption zones, introducing an individual stream of said gaseous mixture into each of said adsorp-l tionzones, removing iromsaidplurality of adsorpticn zones a..r pluralityv of unadsorbed streams of gas each having a different composition. and blending said plurality of unadsorbed lean gases tov form a lean gas product of a predetermined composition.

l2. A method for the dehumidiiication of a humid gas which comprises introducing a humid gas into contact with a downwardly moving bed of adsorbent whereby a iirst portion of said humid gas passes countercurrent to a moving bed of solid granular adsorbent in an adsorption zone to adsorb at least a portion of the moisture therefrom forming a rich adsorbent and leaving a substantially unadsorbed at least partially dehumidied lean gas and a second portion of said humid gas passes concurrently with said rich adsorbent through a desorption zone, removing said lean gas from said adsorption zone, heating said rich adsorbent by indirect heat exchange in said desorption zone while simultaneously stripping the thus heated rich adsorbent with said second portion of said humid gas as a stripping agent thereby forming a partially stripped adsorbent land a desorbed rich gas product, subsequently indirectly cooling said partially stripped adsorbent in a cooling zone7 directly contacting the adsorbent 4while cooling with a portion of said .unadsorbed lean gas forming a cool lean adsorbent, employing said cool lean adsorbent to contact further quantities of said humid gases and `blending at least a portion of said substantially unadsorbed lean gas with at least a portion of said rich gas to provide a gaseous mixture having a predetermined humidity.

13. A method for the dehumidiiication of a humid gas which comprises, introducing said humid gas into Contact with a movingv bed of solid granular adsorbent whereby a rst portion passes countercurrent thereto to adsorb at least a portion oi the moisture therefrom in an adsorption zone forming a rich adsorbent and leaving a substantially unadsorbed and at least partially dehumidied lean gas and a second portion passes concurrently with said rich adsorbent through a desorption zone, separating said unadsorbed gas, subsequently heating said rich adsorbent in said desorption zone by indirect heat exchange While simultaneously stripping the thus heated rich adsorbent with said second portion of said humid gas as a stripping agent forming a partially stripped adsorbent and a desorbed rich gas, subsequenty indirectly cooling said partially stripped. adsorbent in a cooling zone While directly contacting the cooling adsorbent with a portion of said lean gas forming a cool lean adsorbent and a wet gas stream, employing said cool lean adsorbent to contact further quantities of said humid gas and blending at least part of Said wet gas stream with at least part of said lean gas to produce a gaseous mixture having a. predetermined humidity.

14.. A method for the dehumidication of a humid gas which comprises introducing said humid gas into contact with a moving bed of solidl granular adsorbent whereby a first portion of said humid gas passes countercurrent thereto to adsorb a least a portion of the moisture therefrom in an adsorption zone forming a rich adsorbent and leaving a substantially unadsorbed at least partially dehumidied lean gas and a second portion passes concurrently with said rich adsorbent through a desorption zone, separating said unadsorbed lean gas, heating said rich adsorbent by indirectheat exchange while simultaneously stripping the thus heated rich adsorbent with said second. portion of said, humid gas as a stripping agent in said desorption zone forming a partially stripped adsorbent and a desorbed rich gas product, indirectly cooling said partially stripped adsorbent while directly contacting the cooling adsorbent with a portion of said lean gas in a cooling Zone `forming a wet gas stream, employing the cool lean adsorbent to contact further quantities of said humid gas, combining at least part of said wet gas stream with at least part of said descr-bed rich gas stream forming a combined wet gas stream and blending at least part of said combined wet gas stream with at least part of said unadsorbed lean gas toA produce a gaseous mixture having a predetermined humidity.

i5. A process for the separation of a gaseous mixture which comprises establishing a cooling zone, a plurality of adsorption Zones and a desorption zone, passing a moving bed lof compact solid granular adsorbent downwardly through said zones, recirculating adsorbent removed from said desorption zone to said cooling zone, passing a portion of a gaseous mixture to be separated into vContact with said adsorbent whereby first portions of 4said gaseous mixture pass upwardly through each of. said plurality of adsorption zones forming a rich adsorbent containing the more readily adsorbable constituents leaving a plurality of substantially unadsorbed lean gas streams and a second portion of said gaseous mixture passes concurrently with said rich adsorbent into said desorption zone, indirectly heating said rich adsorbent therein while stripping the heated rich adsorbent therein with said lsecond portion or" saidv gaseous mixture to desorb a rich product containingv said more readily adsorbable constituents leaving a hot partially stripped adsorbent, subsequently stripping lsaid partially stripped adsorbent in said cooling zone with a portion of said lean gas while indirectly cooling said adsorbent thereinv to desorb residual quantities of said more readily adsorbable constituents forming a cool lean adsorbent, passing said cool lean adsorbent into said adsorption zone to contact further quantities of said gaseous mixture, removing a plurality of unadsorbed streams oi lean gas each having a diierent composition from said plurality of adsorption zones and blending said plurality of lean gases to form a lean gas product of a predetermined composition.

16. An apparatus for the continuous separation of a gaseous mixture by yselective adsorption on a. solid granular adsorbent which comprises a selective adsorption column provided with anindirect cooling zone, a separation zone andadosorption zone, means for maintainingl a continuous recirculation of .solid granular adsorbent from the bottom to the top of said column and downwardly therethrough as a moving bed through said zones, means for introducing said 4gaseous mixture into the bottom of said separation zone, means for removing a lean gas from the top of said separation zone, means for forcing at least part of said lean gas directly from said adsorption zone through said cooling zone, means for subjecting a rich adsorbent to indirect heating in sai-d desorption zone while concurrently stripping the thus heated adsorbent with a second portion of said gaseous mixture as a stripping gas passed entirely through said desorption zone to desorb adsorbedr more readily adsorbable constituents leaving a hot partially stripped adsorbent, outlet means for removing the thus desorbed rich gas, separate means associated with said outle means for lean gas and with an outlet means rich gas for flowing a lirst portion of said gaseous mixture upwardly through said separation zone and said second portion thereof downwardly through said desorption zone and means in said cooling zone for subjecting said hot partially stripped adsorbent to indirect heat exchange while contacting the cooling adsorbent with said portion of said lean gas forming a cooled lean adsorbent prior to returning said adsorbent to said separation zone.

17. An apparatus according to claim 16 wherein said separation zone comprises at least one adsorption zone each provided with a gas engaging zone and a lean gas disengaging zone.

18. An apparatus for the continuous separation of a gaseous mixture which comprises a selective adsorption column provided at successively lower levels therein with a cooling zone, a. plurality of adsorption zones and a desorption zone, a lift line positioned within said adsorption column adapted to carry adsorbent suspended in a lift gas from the bottom to the top of said adsorption column, means for introducing a portion of said gaseous mixture into each of said adsorption zones, means ior dissipating heat of adsorption liberated therein, means for removing a plurality of streams of substantially unadsorbed gas from said adsorption zones, means for blending the said plurality of streams in various proportions to control the composition of the unadsorbed gas product, means for introducing the remaining portion of said gaseous mixture into said lift line, means for indirectly heating adsorbent in said desorption zone, means for concurrently contacting said heated adsorbent in said desorption zone with a portion of gaseous mixture introduced into said adsorption zone, means for combining constituents desorbed from said adsorbent in said desorption zone with said portion of gaseous mixture introduced into said lift line and means for removing desorbed constituents and lift gas from said adsorption column.

19. An apparatus according to claim 18 wherein said means for heating said adsorbent in said desorption zone and `for cooling said adsorbent in said adsorption zone comprises a coiled nned tube so positioned that the compact moving bed of adsorbent flows downwardly around the coiled tube :and between the fins of said tube.

20. An apparatus for the continuous dehumidifcation of air by selective adsorption on granular charcoal which comprises a vertical selective adsorption column provided with a lift line positioned along the Vertical axis of said column, inlet means to the bottom of said lift line adapted to the introduction of a granular adsorbent and a lift gas to form a suspension, impactless separator means at the top of said lift line in the top of said column adapted to separate suspended adsorbent from said lift gas, said selective adsorption column being further provided with a cooling zone containing a coiled iinned tube heat transfer means adapted to indirectly cool said adsorbent, a separation zone positioned below said cooling zone and containing at least one adsorption zone, means for introducing a stream of air into each of said adsorption zones, means for cooling said adsorbent in each of said adsorption zones, means for removing a stream of dehumidied air from each of said adsorption zones, means for passing a portion of said dehumidied air product through said cooling zone to strip residual moisture therefrom and form a lean cool adsorbent, means for blending the streams of said dehumidied air from each of said adsorption zones in various proportions to control the humidity of said dehumidied air product, said adsorption column being further provided with a desorption zone containing a coiled Iinned tube heat transfer means adapted to indirectly heat said adsorbent, means for concurrently contacting the thus heated adsorbent with a portion of said gaseous mixture to be separated thereby desorbing at least a portion of the adsorbed constituents from said adsorbent, means at the bottom of said lift line for combining said desorbed constituents with said lift gas and means at the top of said adsorption column for removing said lift gas and said desorbed constituents.

2l. An apparatus according to claim 20 wherein said lift line is provided with a lower inlet opening within and positioned adjacent to the bottom of said adsorption column, a movable member adjustable in position with respect to said inlet opening and motive means for moving said movable member whereby said granular adsorbent is introduced uniformly around the periphery of said inlet means and conveyed uniformly through said lift line to control the rate of circulation of said granular adsorbent through said adsorption column.

CLYDE I-I. O. BERG.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,422,007 Soddy July 4, 1922 1,522,480 Allen Jan. 13, 1925 1,825,707 Wagner, Jr Oct. 6, 1931 1,836,301 Bechthold Dec. 15, 1931 2,527,964 Robinson Oct. 31, 1950 2,549,104 Lechthaler Apr. 17, 1951 OTHER REFERENCES Adsorption by C. L. Mantell; McGraw-Hill Book Co., 1945 page 164. 

1. A METHOD FOR THE SEPARATION OF A GASEOUS MIXTURE WHICH COMPRISES PASSING A SOLID GRANULAR ADSORBENT DOWNWARDLY SUCCESSIVELY THROUGH AN ADSORPTION ZONE AND A DESORPTION ZONE AS A MOVING BED, INTRODUCING SAID GASEOUS MIXTURE INTO CONTACT WITH SAID ADSORBENT WHEREBY A FIRST PORTION PASSES COUNTERCURRENTLY THROUGH SAID ADSORPTION ZONE WHEREIN THE MORE READILY ADSORBABLE CONSTITUENTS ARE ADSORBED TO FORM A RICH ADSORBENT AND LEAVING LESS READILY ADSORBABLE CONSTITUENTS AS A SUBSTANTIALLY UNADSORBED LEAN GAS AND A SECOND PORTION PASSES CONCURRENTLY WITH SAID RICH ADSORBENT THROUGH SAID DESORPTION ZONE, SUBJECTING SAID RICH ADSORBENT THEREIN TO 